EP2687266A1 - Colour intensification by means of polyacrylate - Google Patents

Abstract

Agent (A) comprises (a) at least one acrylic acid copolymer containing at least one carbonyl group containing structural unit (T) and at least one alkane group containing structural unit (III) and (b) at least one color changing compound, in a carrier. Agent (A) comprises (a) at least one acrylic acid copolymer containing at least one carbonyl group containing structural unit (T) of formula -(CH 2-C(R1)(C(=O)OM))- (I) or at least one structural Unit of formula -(CH 2-C(R2)(C(=O)-O-R3))- (II) and at least one alkane group containing structural unit of formula -(CH 2-C(R4)(R5))- (III) and (b) at least one color changing compound, in a carrier. R1, R2, R4 : H or 1-6C-alkyl; R3 : 1-20C-alkyl, 2-6C-alkenyl, 2-6C-hydroxyalkyl or 2-6C-polyhydroxyalkyl; R5 : H, 1-6C-alkyl or phenyl; and M : H, Na, K, (0.5)Mg or (0.5)Ca. An independent claim is included for coloring and/or brightening keratin fibers comprising optionally applying a pretreatment agent (M1) on the fiber, further applying a coloring and/or a brightening (M2) on the fiber, where optionally a further agent (M3) is added to M2 before application, rinsing (M2) after 5-30 minutes on the fiber and optionally subsequently applying a treating agent (M4) on the fiber after treating and rinsing after 2-25 minutes, where M2 is (A).

Description

The present invention relates to agents for dyeing and / or whitening keratinic fibers, in particular human hair, which contain special acrylic acid copolymers. Furthermore, the invention relates to the use of these agents for improving the color lift in the dyeing of keratinic fibers, their use for improving the washing stability of dyed keratinic fibers and a corresponding method.

Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

In addition to bleaching agents which cause an oxidative lightening of the hair by degradation of natural hair dyes, three types of hair dyes are of importance in the field of hair coloration: For permanent, intensive colorations with corresponding fastness properties so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation stains are characterized by excellent, long lasting staining results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly. Finally, recently, a novel dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In such processes, for example, 5,6-dihydroxyindoline is used as the dye precursor. In, in particular multiple, application of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The coloration can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors. After the dyeing process, the hair is exposed to a variety of environmental stresses over a long period of time. These range from the daily weathering of the hair, for example by sun rays and hair washes, over mechanical, caused by the styling stresses to chemical influences, if the consumer subjects the hair to a subsequent hair dyeing or shaping process. The environmental influences have great effects not only on the hair structure itself but also on the dyes present in the hair after the dyeing process. The dyes can fade by exposure, or washed out of the hair by sweat or shampooing. These properties are referred to as the fastness properties of the dyes. If the dyes formed or used directly in the course of color formation have significantly different fastnesses (eg UV stability, perspiration fastness, washfastness, etc.), then a noticeable and therefore undesirable color shift can occur over time. Both the occurrence of color shifts and in particular the washing caused by fading of the dyeings is undesirable by the consumer.

There are several ways to reduce the intensity loss of hair dyes caused by repeated washing. By striving for a staining result that is as intensive as possible from the outset, the intensity drop perceived by the consumer can be delayed. A second possibility is the improvement of the color content through the use of active ingredients which inhibit or reduce the washing out of the dyes. Of particular advantage is the discovery of an active ingredient or a combination of active ingredients, which both improves the color absorption capacity of the dyes during the dyeing process as well as their subsequent leaching minimized during subsequent shampooing.

The object of the present invention is therefore to provide means for dyeing and / or whitening keratinic fibers, which improve the color lift during dyeing and enhance the penetration of dyes or dye precursors into the keratinic fibers. Furthermore, a leaching of the dyes in the course of repeated shampooing should be prevented or minimized. The compositions according to the invention are intended to improve color intensity and wash fastness, without possessing the disadvantages inherent in the colorants already known from the prior art.

In addition, dyeings should also be obtained with these agents, which have a favorable performance profile in terms of their further fastness properties, such as their light, friction, welding and cold wave fastness. Finally, it is particularly desirable to provide colorants with good leveling power.

In the cosmetics market the optimization of the color content is of great importance, different color protection shampoos or conditioners already exist in the market. Various substances are known from the prior art, which are used for color protection of already colored hair. In particular polymers find application with this objective.

" Silicones Used in Permanent and Semi-Permanent Hair Dyes to Reduce the Fading and Color Change Process of Dyed Hair Occuring by Wash-Out or UV Radiation ", J. Cosmetic Sci., (2004) 55 (Supplement), pp. 123-131 , describes the use of silicones to improve color retention. US Pat. No. 7,066,966 and US Pat. No. 7,147,672 disclose an oxidative dyeing composition having good washfastnesses containing a cationic polyvinyl lactam. US 2011/0219552 A1 discloses a method of protecting dyed hair from washout using hydrophobized cationic polymers. Finally, the concerns US 2011/0044924 Compositions and methods for increasing the color intensity and color protection of colored hairs containing quaternary ammonium salts.

1. (a) mindestens ein Acrylsäure-Copolymer enthaltend mindestens eine Struktureinheit der allgemeinen Formel (I), mindestens eine Struktureinheit der allgemeinen Formel (II) und mindestens eine Struktureinheit der allgemeinen Formel (III),
   
   worin

   R1, R2, R4

   unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,

   R3

   für eine C₁-C₂₀-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe oder eine C₂-C₆-Polyhydroxyalkylgruppe steht,

   R5

   für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe oder eine Phenylgruppe steht,

   M

   für ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium steht, und

2. (b) mindestens eine farbverändernde Verbindung.

However, the use of these known from the prior art polymers is often associated with disadvantages. Surprisingly, it has now been found that hair treatment compositions containing specific acrylic acid copolymers fulfill the above-described task in an optimum manner, without being associated with the disadvantages known from the prior art. A first subject of the present invention are therefore agents for dyeing and / or whitening keratinic fibers, in particular human hair, contained in a cosmetic carrier

1. (a) at least one acrylic acid copolymer comprising at least one structural unit of the general formula (I), at least one structural unit of the general formula (II) and at least one structural unit of the general formula (III),
   
   wherein

   R1, R2, R4

   independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group,

   R3

   is a C ₁ -C ₂₀ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group,

   R5

   represents a hydrogen atom, a C ₁ -C ₆ -alkyl group or a phenyl group,

   M

   is a hydrogen atom or for sodium, potassium, ½ magnesium or ½ calcium, and

2. (b) at least one color-changing compound.

In principle, all animal hair, e.g. Wool, horsehair, angora hair, furs, feathers and products or textiles made from them. Preferably, however, the keratinic fibers are human hairs.

The term "dyeing of keratin fibers" used in the invention includes any form of color change of the fibers. In particular, the color changes encompassed by the terms tinting, whitening, bleaching, bleaching, oxidative dyeing, semipermanent dyeing, permanent dyeing and temporary dyeing are included. Explicitly encompassed according to the invention are color changes which have a lighter color result in comparison to the starting color, for example coloring bleaching operations.

As a first essential ingredient, the compositions according to the invention contain at least one acrylic acid copolymer containing at least one structural unit of the general formula (I), at least one structural unit of the general formula (II) and at least one structural unit of the general formula (III).

Thus, in the context of the present invention, the acrylic acid copolymer is a copolymer which can be prepared by copolymerization of at least one acrylic acid or methacrylic acid monomer, at least one acrylic acid ester or methacrylic acid ester monomer and at least one optionally substituted ethene monomer.

In the course of the work leading to this invention, it has been found that the object according to the invention can be achieved in particular if different acrylate or methacrylic acid ester monomers and various ethene monomers are used in the copolymerization to give the acrylic acid copolymer according to the invention.

The acrylic acid copolymer according to the invention has advantageous properties in particular if at least three different acrylate or methacrylic acid ester monomers and two different ethene monomers are used in the copolymerization to give the acrylic acid copolymer according to the invention.

Accordingly, the means for dyeing and / or lightening keratinic fibers containing at least one acrylic acid copolymer, at least one structural unit of the general formula (I), at least three different structural units of the general formula (II) and at least two different structural units of the general formula (III).

worin

R1, R2', R2", R2"', R4', R4"

unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,

R3', R3", R3"'

unabhängig voneinander für für eine C₁-C₂₀-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe oder eine C₂-C₆-Polyhydroxyalkylgruppe stehen,

R5', R5"

unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe oder eine Phenylgruppe stehen,

M

für ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium steht,

mit der Maßgabe, dass R3', R3" und R3"' voneinander verschiedene Reste darstellen und
mit der Maßgabe, das R5' und R5" voneinander verschiedene Reste darstellen.In a preferred embodiment of the first subject of the invention, the means for dyeing and / or whitening keratinic fibers are therefore characterized in that the acrylic copolymer containing in the middle at least one structural unit of the general formula (I), at least one structural unit of the general formula (IIa) , at least one structural unit of the general formula (IIb), at least one structural unit of the general formula (IIc), at least one structural unit of the general formula (IIIa) and at least one structural unit of the general formula (IIIb),

wherein

R1, R2 ', R2 ", R2"', R4 ', R4 "

independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group,

R3 ', R3 ", R3"'

independently of one another represent a C ₁ -C ₂₀ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group,

R5 ', R5 "

independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group or a phenyl group,

M

represents a hydrogen atom or represents sodium, potassium, ½ magnesium or ½ calcium,

with the proviso that R3 ', R3 "and R3"' represent different radicals from one another and
with the proviso that R5 'and R5 "represent radicals other than one another.

The following are examples of the substituents R1, R2, R2 ', R2 mentioned in the formulas (I), (II), (IIa), (IIb), (IIc), (III), (IIIa) and (IIIb) Examples of C ₁ -C ₆ -alkyl groups are -CH ₃ , -, R 2 ", R ₃ , R _{3 '} , R _3" , R ₃ "', R _4, R _{4 ',} R _4", R 5, R 5' and R 5 ". CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , - (CH ₂ ) ₄ CH ₃ , - (CH ₂ ) ₅ CH ₃ . Particularly preferred alkyl radicals are methyl, ethyl and -CH ₂ CH ₂ CH ₂ CH ₃ - examples of C ₆ -C ₂₀ alkyl groups are hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradeyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl. Examples of C ₂ -C ₆ -alkenyl groups are vinyl, prop-2-enyl (allyl), 2-methyl-prop-2-enyl, but-3-enyl, but-2-enyl, pent-4-enyl or pent -3-enyl. Examples of C ₂ -C ₆ -hydroxyalkyl groups are -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, where the group -CH ₂ CH ₂ OH is preferred. Examples of C ₂ -C ₆ -polyhydroxyalkyl groups are 1,2-dihydroxyethyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl and the 2,4-dihydroxybutyl.

The general formula (I) is a structural unit of the acrylic acid copolymer of the present invention obtained by using an acrylic acid or methacrylic acid monomer in the copolymerization. M in formula (I) is preferably a hydrogen atom.

Depending on the pH of the cosmetic carrier, however, the acid function in formula (I) may also be deprotonated in the form of a negatively charged carboxyl group. In this case, M is a cation present to neutralize the carboxy group selected from sodium, potassium, ½ magnesium or ½ calcium. When M is sodium or potassium, it is preferred.

Furthermore, it is preferred if the radicals R 1 and R 2 of the structural units of the general formula (I) and (II) independently of one another represent a methyl group or a hydrogen atom.

The radical R 3 of the structural unit of the general formula (II) preferably represents one for a C ₁ -C ₂₀ -alkyl group.

It is also preferred that the radical R 4 of the structural unit of the general formula (III) is a hydrogen atom and R 5 is a hydrogen atom or a phenyl group.

In addition, it is particularly advantageous in the context of the present invention if the radicals R 1 and R 2 'are a methyl group and the radicals R 2 ", R 2"', R 4 ', R 4 "and R 5' are a hydrogen atom.

Acrylic acid copolymers according to the invention having particularly advantageous properties are obtained especially when the radicals R 3 ', R 3 "and R 3"' represent three different C ₁ -C ₂₀ -alkyl groups. Particularly preferably, R3 'is a methyl group, R 3 "is an ethyl group and R3"' is a n-butyl group (ie a group -CH ₂ CH ₂ CH ₂ CH _3).

Furthermore, it is particularly preferred that the radical R5 'is a hydrogen atom and the radical R5 "is a phenyl group.

In a further preferred embodiment of the first subject of the invention, the means for dyeing and / or lightening keratinic fibers are therefore characterized in that the radicals R 1, R 2 'and R 3' represent a methyl group, the radicals R 2 ", R 2" ', R 4' , R4 "and R5 'represent a hydrogen atom, R3" represents an ethyl group, R3 "' represents an n-butyl group and R5" represents a phenyl group.

Preferred and particularly preferred representatives of the acrylic acid copolymers containing in the agent according to the invention are characterized in that they contain at least one structural unit of the general formula (I), at least one structural unit of the general formula (IIa), at least one structural unit of the general formula (IIb), at least a structural unit of the general formula (IIc), at least one structural unit of the general formula (IIIa) and at least one structural unit of the general formula (IIIb), wherein the radicals R1, R2 ', R2 "and R2"' independently of one another represent a hydrogen atom or are a methyl group and the radicals R3 ', R3 ", R3"', R4 ', R4 ", R5' and R5" stand for a substituent combination selected from R3 ' R3 " R3 '" R4 ' R4 " R5 ' R5 " 1 CH ₃ C ₂ H ₅ C ₃ H ₇ H H H phenyl 2 CH ₃ C ₂ H ₅ C ₄ H ₉ H H H phenyl 3 CH ₃ C ₂ H ₅ C ₅ H ₁₁ H H H phenyl 4 CH ₃ C ₂ H ₅ C ₁₂ H ₂₅ H H H phenyl 5 CH ₃ C ₂ H ₅ C ₁₄ H ₂₉ H H H phenyl 6 CH ₃ C ₂ H ₅ C ₁₆ H ₃₃ H H H phenyl 7 CH ₃ C ₂ H ₅ C ₁₈ H ₃₇ H H H phenyl 8th CH ₃ C ₃ H ₇ C ₄ H ₉ H H H phenyl 9 CH ₃ C ₃ H ₇ C ₅ H ₁₁ H H H phenyl 10 CH ₃ C ₃ H ₇ C ₁₂ H ₂₅ H H H phenyl 11 CH ₃ C ₃ H ₇ C ₁₄ H ₂₉ H H H phenyl 12 CH ₃ C ₃ H ₇ C ₁₆ H ₃₃ H H H phenyl 13 CH ₃ C ₃ H ₇ C ₁₈ H ₃₇ H H H phenyl 14 CH ₃ C ₃ H ₇ C ₃ H ₇ H H H phenyl 15 CH ₃ C ₄ H ₉ C ₅ H ₁₁ H H H phenyl 16 CH ₃ C ₄ H ₉ C ₁₂ H ₂₅ H H H phenyl 17 CH ₃ C ₄ H ₉ C ₁₄ H ₂₉ H H H phenyl 18 CH ₃ C ₄ H ₉ C ₁₆ H ₃₃ H H H phenyl 19 CH ₃ C ₄ H ₉ C ₁₈ H ₃₇ H H H phenyl 20 CH ₃ C ₅ H ₁₁ C ₁₂ H ₂₅ H H H phenyl 21 CH ₃ C ₅ H ₁₁ C ₁₄ H ₂₉ H H H phenyl 22 CH ₃ C ₅ H ₁₁ C ₁₆ H ₃₃ H H H phenyl 23 CH ₃ C ₅ H ₁₁ C ₁₈ H ₃₇ H H H phenyl 24 C ₂ H ₅ C ₃ H ₇ C ₄ H ₉ H H H phenyl 25 C ₂ H ₅ C ₃ H ₇ C ₅ H ₁₁ H H H phenyl 26 C ₂ H ₅ C ₃ H ₇ C ₁₂ H ₂₅ H H H phenyl 27 C ₂ H ₅ C ₃ H ₇ C ₁₄ H ₂₉ H H H phenyl 28 C ₂ H ₅ C ₃ H ₇ C ₁₆ H ₃₃ H H H phenyl 29 C ₂ H ₅ C ₃ H ₇ C ₁₈ H ₃₇ H H H phenyl 30 C ₂ H ₅ C ₄ H ₉ C ₅ H ₁₁ H H H phenyl 31 C ₂ H ₅ C ₄ H ₉ C ₁₂ H ₂₅ H H H phenyl 32 C ₂ H ₅ C ₄ H ₉ C ₁₄ H ₂₉ H H H phenyl 33 C ₂ H ₅ C ₄ H ₉ C ₁₆ H ₃₃ H H H phenyl 34 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ H H H phenyl 35 C ₃ H ₇ C ₄ H ₉ C ₁₂ H ₂₅ H H H phenyl 36 C ₃ H ₇ C ₄ H ₉ C ₁₄ H ₂₉ H H H phenyl 37 C ₃ H ₇ C ₄ H ₉ C ₁₆ H ₃₃ H H H phenyl 38 C ₃ H ₇ C ₄ H ₉ C ₁₈ H ₃₇ H H H phenyl 39 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ H H H phenyl 40 CH ₃ C ₂ H ₅ C ₃ H ₇ CH ₃ H H phenyl 41 CH ₃ C ₂ H ₅ C ₄ H ₉ CH ₃ H H phenyl 42 CH ₃ C ₂ H ₅ C ₅ H ₁₁ CH ₃ H H phenyl 43 CH ₃ C ₂ H ₅ C ₁₂ H ₂₅ CH ₃ H H phenyl 44 CH ₃ C ₂ H ₅ C ₁₄ H ₂₉ CH ₃ H H phenyl 45 CH ₃ C ₂ H ₅ C ₁₆ H ₃₃ CH ₃ H H phenyl 46 CH ₃ C ₂ H ₅ C ₁₈ H ₃₇ CH ₃ H H phenyl 47 CH ₃ C ₃ H ₇ C ₄ H ₉ CH ₃ H H phenyl 48 CH ₃ C ₃ H ₇ C ₅ H ₁₁ CH ₃ H H phenyl 49 CH ₃ C ₃ H ₇ C ₁₂ H ₂₅ CH ₃ H H phenyl 50 CH ₃ C ₃ H ₇ C ₁₄ H ₂₉ CH ₃ H H phenyl 51 CH ₃ C ₃ H ₇ C ₁₆ H ₃₃ CH ₃ H H phenyl 52 CH ₃ C ₃ H ₇ C ₁₈ H ₃₇ CH ₃ H H phenyl 53 CH ₃ C ₃ H ₇ C ₃ H ₇ CH ₃ H H phenyl 54 CH ₃ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H phenyl 55 CH ₃ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H phenyl 56 CH ₃ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H phenyl 57 CH ₃ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H phenyl 58 CH ₃ C ₄ H ₉ C ₁₈ H ₃₇ CH ₃ H H phenyl 59 CH ₃ C ₅ H ₁₁ C ₁₂ H ₂₅ CH ₃ H H phenyl 60 CH ₃ C ₅ H ₁₁ C ₁₄ H ₂₉ CH ₃ H H phenyl 61 CH ₃ C ₅ H ₁₁ C ₁₆ H ₃₃ CH ₃ H H phenyl 62 CH ₃ C ₅ H ₁₁ C ₁₈ H ₃₇ CH ₃ H H phenyl 63 C ₂ H ₅ C ₃ H ₇ C ₄ H ₉ CH ₃ H H phenyl 64 C ₂ H ₅ C ₃ H ₇ C ₅ H ₁₁ CH ₃ H H phenyl 65 C ₂ H ₅ C ₃ H ₇ C ₁₂ H ₂₅ CH ₃ H H phenyl 66 C ₂ H ₅ C ₃ H ₇ C ₁₄ H ₂₉ CH ₃ H H phenyl 67 C ₂ H ₅ C ₃ H ₇ C ₁₆ H ₃₃ CH ₃ H H phenyl 68 C ₂ H ₅ C ₃ H ₇ C ₁₈ H ₃₇ CH ₃ H H phenyl 69 C ₂ H ₅ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H phenyl 70 C ₂ H ₅ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H phenyl 71 C ₂ H ₅ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H phenyl 72 C ₂ H ₅ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H phenyl 73 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H phenyl 74 C ₃ H ₇ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H phenyl 75 C ₃ H ₇ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H phenyl 76 C ₃ H ₇ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H phenyl 77 C ₃ H ₇ C ₄ H ₉ C ₁₈ H ₃₇ CH ₃ H H phenyl 78 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H phenyl 79 CH ₃ C ₂ H ₅ C ₃ H ₇ H H H CH ₃ 80 CH ₃ C ₂ H ₅ C ₄ H ₉ H H H CH ₃ 81 CH ₃ C ₂ H ₅ C ₅ H ₁₁ H H H CH ₃ 82 CH ₃ C ₂ H ₅ C ₁₂ H ₂₅ H H H CH ₃ 83 CH ₃ C ₂ H ₅ C ₁₄ H ₂₉ H H H CH ₃ 84 CH ₃ C ₂ H ₅ C ₁₆ H ₃₃ H H H CH ₃ 85 CH ₃ C ₂ H ₅ C ₁₈ H ₃₇ H H H CH ₃ 86 CH ₃ C ₃ H ₇ C ₄ H ₉ H H H CH ₃ 87 CH ₃ C ₃ H ₇ C ₅ H ₁₁ H H H CH ₃ 88 CH ₃ C ₃ H ₇ C ₁₂ H ₂₅ H H H CH ₃ 89 CH ₃ C ₃ H ₇ C ₁₄ H ₂₉ H H H CH ₃ 90 CH ₃ C ₃ H ₇ C ₁₆ H ₃₃ H H H CH ₃ 91 CH ₃ C ₃ H ₇ C ₁₈ H ₃₇ H H H CH ₃ 92 CH ₃ C ₃ H ₇ C ₃ H ₇ H H H CH ₃ 93 CH ₃ C ₄ H ₉ C ₅ H ₁₁ H H H CH ₃ 94 CH ₃ C ₄ H ₉ C ₁₂ H ₂₅ H H H CH ₃ 95 CH ₃ C ₄ H ₉ C ₁₄ H ₂₉ H H H CH ₃ 96 CH ₃ C ₄ H ₉ C ₁₆ H ₃₃ H H H CH ₃ 97 CH ₃ C ₄ H ₉ C ₁₈ H ₃₇ H H H CH ₃ 98 CH ₃ C ₅ H ₁₁ C ₁₂ H ₂₅ H H H CH ₃ 99 CH ₃ C ₅ H ₁₁ C ₁₄ H ₂₉ H H H CH ₃ 100 CH ₃ C ₅ H ₁₁ C ₁₆ H ₃₃ H H H CH ₃ 101 CH ₃ C ₅ H ₁₁ C ₁₈ H ₃₇ H H H CH ₃ 102 C ₂ H ₅ C ₃ H ₇ C ₄ H ₉ H H H CH ₃ 103 C ₂ H ₅ C ₃ H ₇ C ₅ H ₁₁ H H H CH ₃ 104 C ₂ H ₅ C ₃ H ₇ C ₁₂ H ₂₅ H H H CH ₃ 105 C ₂ H ₅ C ₃ H ₇ C ₁₄ H ₂₉ H H H CH ₃ 106 C ₂ H ₅ C ₃ H ₇ C ₁₆ H ₃₃ H H H CH ₃ 107 C ₂ H ₅ C ₃ H ₇ C ₁₈ H ₃₇ H H H CH ₃ 108 C ₂ H ₅ C ₄ H ₉ C ₅ H ₁₁ H H H CH ₃ 109 C ₂ H ₅ C ₄ H ₉ C ₁₂ H ₂₅ H H H CH ₃ 110 C ₂ H ₅ C ₄ H ₉ C ₁₄ H ₂₉ H H H CH ₃ 111 C ₂ H ₅ C ₄ H ₉ C ₁₆ H ₃₃ H H H CH ₃ 112 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ H H H CH ₃ 113 C ₃ H ₇ C ₄ H ₉ C ₁₂ H ₂₅ H H H CH ₃ 114 C ₃ H ₇ C ₄ H ₉ C ₁₄ H ₂₉ H H H CH ₃ 115 C ₃ H ₇ C ₄ H ₉ C ₁₆ H ₃₃ H H H CH ₃ 116 C ₃ H ₇ C ₄ H ₉ C ₁₈ H ₃₇ H H H CH ₃ 117 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ H H H CH ₃ 118 CH ₃ C ₂ H ₅ C ₃ H ₇ CH ₃ H H CH ₃ 119 CH ₃ C ₂ H ₅ C ₄ H ₉ CH ₃ H H CH ₃ 120 CH ₃ C ₂ H ₅ C ₅ H ₁₁ CH ₃ H H CH ₃ 121 CH ₃ C ₂ H ₅ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 122 CH ₃ C ₂ H ₅ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 123 CH ₃ C ₂ H ₅ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 124 CH ₃ C ₂ H ₅ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 125 CH ₃ C ₃ H ₇ C ₄ H ₉ CH ₃ H H CH ₃ 126 CH ₃ C ₃ H ₇ C ₅ H ₁₁ CH ₃ H H CH ₃ 127 CH ₃ C ₃ H ₇ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 128 CH ₃ C ₃ H ₇ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 129 CH ₃ C ₃ H ₇ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 130 CH ₃ C ₃ H ₇ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 131 CH ₃ C ₃ H ₇ C ₃ H ₇ CH ₃ H H CH ₃ 132 CH ₃ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H CH ₃ 133 CH ₃ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 134 CH ₃ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 135 CH ₃ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 136 CH ₃ C ₄ H ₉ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 137 CH ₃ C ₅ H ₁₁ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 138 CH ₃ C ₅ H ₁₁ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 139 CH ₃ C ₅ H ₁₁ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 140 CH ₃ C ₅ H ₁₁ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 141 C ₂ H ₅ C ₃ H ₇ C ₄ H ₉ CH ₃ H H CH ₃ 142 C ₂ H ₅ C ₃ H ₇ C ₅ H ₁₁ CH ₃ H H CH ₃ 143 C ₂ H ₅ C ₃ H ₇ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 144 C ₂ H ₅ C ₃ H ₇ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 145 C ₂ H ₅ C ₃ H ₇ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 146 C ₂ H ₅ C ₃ H ₇ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 147 C ₂ H ₅ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H CH ₃ 148 C ₂ H ₅ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 149 C ₂ H ₅ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 150 C ₂ H ₅ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 151 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H CH ₃ 152 C ₃ H ₇ C ₄ H ₉ C ₁₂ H ₂₅ CH ₃ H H CH ₃ 153 C ₃ H ₇ C ₄ H ₉ C ₁₄ H ₂₉ CH ₃ H H CH ₃ 154 C ₃ H ₇ C ₄ H ₉ C ₁₆ H ₃₃ CH ₃ H H CH ₃ 155 C ₃ H ₇ C ₄ H ₉ C ₁₈ H ₃₇ CH ₃ H H CH ₃ 156 C ₃ H ₇ C ₄ H ₉ C ₅ H ₁₁ CH ₃ H H CH ₃

A particularly preferred acrylic acid copolymer is the polyacrylate-15 known under the INCI name.

A further particularly preferred embodiment of the first subject of the invention is therefore an agent according to the invention which is characterized in that it contains polyacrylate-15 as the acrylic acid copolymer.

The compositions according to the invention for dyeing and / or lightening keratinic fibers contain the acrylic acid copolymer (s) in a total amount of from 0.001 to 25% by weight, preferably from 0.01 to 15% by weight, more preferably from 0.1 to 10% by weight, and more preferably from 0.5 to 5% by weight, based on the ready-to-use agent.

A further preferred embodiment of the first subject of the invention is therefore an agent for dyeing and / or whitening keratinic fibers, which is characterized in that it contains the acrylic acid copolymer (s) (a) in a total amount of 0.001 to 25 wt. -%, preferably from 0.01 to 15 wt .-%, particularly preferably from 0.1 to 10% by weight and particularly preferably from 0.5 to 5 wt .-% - based on the ready-to-use agent - contains.

As a second essential ingredient, the agents according to the invention contain at least one color-changing compound. In the context of the present invention, a color-changing compound is understood as meaning a compound or a substance by means of which the color of the keratinic fibers can be changed. Included within this definition are both compounds which alter the keratinic fibers towards a darker hue, as well as compounds, after which the keratinic fibers have a lighter shade than the original hue. Included within the definition of the color-changing compound are oxidation dye precursors, direct dyes, dye precursors of naturally-colored dyes, and oxidizers.

If the agent according to the invention contains at least one oxidation dye precursor and / or at least one substantive dye in addition to the acrylic acid copolymer as the color-changing compound, this is preferred.

A further preferred embodiment of the first subject of the invention is therefore an agent according to the invention which is characterized in that it comprises as color-changing compound at least one oxidation dye precursor and / or at least one substantive dye, in each case in an amount of 0.001 to 12 wt .-%, preferably from 0.01 to 10 wt .-%, particularly preferably from 0.1 to 5 wt .-% and particularly preferably from 0.25 to 3 wt .-% - based on the ready-to-use agent - contains.

Among the oxidation dye precursors are developer type and coupler type oxidation dye precursors. Particularly suitable developer-type oxidation dye precursors are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl ) -p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H- imidazol-1-yl) propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1 , 10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( 1,2-dihydroxyethyl) phenol, 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2 , 5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] p yrazol-1-one and their physiologically acceptable salts.

Particularly suitable coupler-type oxidation dye precursors are selected from the group formed from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino 4-chloro-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2.6 Bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2- Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholine-4 -ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methyl-amino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or their physiologically acceptable salts ,

Within the scope of the work leading to this invention, it has been found that the task according to the invention is particularly satisfied with agents containing certain developer / coupler combinations. Therefore, means of coloring keratinic fibers are in addition to the acrylic acid copolymer according to the invention contain certain combinations of oxidation dye precursors, particularly preferred.

It is preferred if the compositions according to the invention contain the acrylic acid copolymer one of the following developer / coupler combinations: p-toluenediamine / resorcinol p-toluenediamine / 2-methylresorcinol; p-toluenediamine / 2-amino-3-hydroxypyridine p-toluenediamine / 2,7-dihydroxynaphthalene; p-toluenediamine / 3-aminophenol; p-toluenediamine / 1-naphthol; p-toluenediamine / 1,5-dihydroxynaphthalene; p-toluenediamine / 5-amino-2-methylphenol; p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol; p-toluenediamine / 3-amino-2-chloro-6-methylphenol; p-toluenediamine / 2,6-dihydroxy-3,4-dimethylpyridine; p-toluenediamine / 3-amino-2-methylamino-6-methoxypyridine; p-toluenediamine / 1,3-bis (2,4-diaminophenyl) propane 2,4,5,6-tetraaminopyrimidine / resorcinol; 2,4,5,6-tetraaminopyrimidine / 2-methylresorcinol 2,4,5,6-tetraaminopyrimidine / 2-amino-3-hydroxypyridine; 2,4,5,6-tetraaminopyrimidine / 2,7-dihydroxynaphthalene; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2,7-dihydroxynaphthalene; p-aminophenol / resorcinol p-aminophenol / 2-methylresorcinol; p-aminophenol / 2-amino-3-hydroxypyridine; p-aminophenol / 2,7-dihydroxynaphthalene; p-aminophenol / 3-aminophenol; p-aminophenol / 1-naphthol; p-aminophenol / 1,5-dihydroxynaphthalene; p-aminophenol / 5-amino-2-methylphenol; p-aminophenol / 2- (2,4-diaminophenoxy) ethanol; p-aminophenol / 3-amino-2-chloro-6-methylphenol; p-aminophenol / 2,6-dihydroxy-3,4-dimethylpyridine; p-aminophenol / 3-amino-2-methylamino-6-methoxypyridine p-aminophenol / 1,3-bis (2,4-diaminophenyl) propane.

Particularly preferred agents according to the invention contain, in addition to the acrylic acid copolymer, one of the following combinations of two developers and one coupler: p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / resorcinol; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2-methylresorcinol; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2-amino-3-hydroxypyridine; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2,7-dihydroxynaphthalene.

In particular, a particularly good color intensification or a particularly good color retention is achieved if the keratinic fibers are dyed with a formulation which contains as color-changing compounds a combination of p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, resorcinol, 2 Methylresorcinol, 2-amino-3-hydroxypridine and 2,7-dihydroxynaphthalene.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.

Within the scope of a further preferred embodiment, the agent according to the invention contains at least one substantive dye as the color-changing compound. These are dyes that raise directly on the hair and no oxidative process to form the Need color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

Direct dyes may be subdivided into anionic, cationic and nonionic substantive dyes which are selected and used by those skilled in the art according to the requirements of the carrier base.

Preferred anionic substantive dyes are those having the international designations or trade names bromophenol blue, tetrabromophenol blue, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Preferred cationic substantive dyes are Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), Basic Blue 99, Basic Brown 16 and Basic Brown 17 and Yellow 87, Basic Orange 31 and Basic Red 51.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- Chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro 6-ethylamino-4-nitrophenol.

It is preferred if the erfindungsgmäße agent as the color-changing compound contains the substantive dye 4-amino-3-nitrophenol either alone or in combination with other color-changing compounds.

In a further preferred embodiment, the agents according to the invention contain as color-changing compounds both a substantive dye and a developer-type and / or coupler-type oxidation dye precursor.

It is likewise possible that the composition according to the invention contains as color-changing compound at least one dye precursor of a naturally-analogous dye. As dye precursors of naturally-analogous dyes it is preferred to use indoles and indolines which have at least two groups selected from hydroxyl and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

The agent according to the invention contains at least one color-changing compound in each case in an amount of 0.001 to 12% by weight. If the color-modifying agent is oxidation dye precursors, substantive dyes and / or precursors of naturally-analogous dyes, they are preferably each contained in a weight fraction of from 0.01 to 10% by weight, particularly preferably from 0.1 to 5% by weight. We particularly preferred from 0.25 to 3 wt .-% - based on the ready-to-use agent - used.

The compositions according to the invention can furthermore be used as brightening colorants or as brighteners. To achieve the whitening effect, the agents contain an oxidizing agent as color-changing compound. Hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds is preferably used as the oxidizing agent. Examples of such addition products are addition products of urea, melamine and sodium borate.

In a preferred embodiment, hydrogen peroxide itself is used as the aqueous solution. The concentration of a hydrogen peroxide solution in the composition according to the invention is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6 to 12 wt .-% solutions are used in water. If the color-modifying agent is an oxidizing agent, it may be present in an amount of 0.001 to 12% by weight, based on the ready-to-use agent. According to the invention, ready-to-use agents of the first subject of the invention are characterized in that they are 0.01 to 10 wt .-%, preferably 1 to 9 wt .-%, particularly preferably 2.5 to 8 wt .-% and in particular 3 to 6 wt. % Hydrogen peroxide, based in each case on the total weight of the composition.

A further preferred embodiment of the first subject of the invention is therefore an agent according to the invention which is characterized in that it contains as color-changing compound at least one oxidizing agent selected from hydrogen peroxide and its solid addition products of organic or inorganic compounds, in an amount of 0.001 to 12% by weight. %, preferably from 0.01 to 10 wt .-%, preferably 1 to 9 wt .-%, particularly preferably 2.5 to 8 wt .-% and in particular 3 to 6 wt .-% - based on the ready-to-use agent - contains.

Such oxidizer formulations are preferably aqueous, flowable oxidizer formulations. Preferred preparations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77, 5 wt .-% and in particular 65 to 75 wt .-% water.

In a further preferred embodiment, the agents according to the invention as color-changing compounds comprise both a developer-type and / or a coupler-type oxidation dye precursor and an oxidizing agent.

To achieve enhanced whitening and bleaching action, the composition may further contain at least one peroxo salt. Suitable peroxo salts are inorganic peroxo compounds, preferably selected from the group formed from ammonium peroxodisulfate, alkali metal peroxodisulfates, ammonium peroxomonosulfate, alkali metal peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides. Particularly preferred are peroxodisulfates, in particular ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

If the agents according to the invention additionally contain persulfates, these are in a total amount of 0.01 to 30 wt .-%, preferably 1.5 to 28 wt .-%, preferably 2.0 to 25 wt .-%, and in particular preferably to 5 to 20 wt .-%, each based on the total weight of the ready-to-use agent included.

The agent may contain further bleach boosters to enhance the bleaching effect, such as tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), tetraacetylglycoluril (TAGU), N-nonanoylsuccinimide ( NOSI), n-nonanoyl or isononanoyloxybenzenesulfonate (n- or i-NOBS), phthalic anhydride, triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and carbonate salts or bicarbonate salts, in particular ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate , Potassium hydrogencarbonate, dipotassium carbonate and calcium carbonate, and nitrogen-containing heterocyclic bleach boosters such as 4-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, and N-methyl-3,4-dihydroisoquinolinium-p -toluolsulfonat.

To further increase the lightening, at least one SiO ₂ compound, such as silica or silicates, in particular water glasses, may additionally be added to the composition according to the invention. It may be preferred according to the invention, the SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, more preferably in amounts of 0.15 wt .-% to 10 wt .-% and most preferably in amounts of from 0.2% by weight to 5% by weight, based in each case on the anhydrous composition according to the invention. The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again. Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Common and preferred in the context of the present invention, complexing agents and stabilizers are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS), hydroxyethyliminodiacetic acid, Nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di (2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), ethylenediaminediglutaric acid (EDGA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG), 2-hydroxypropylenediamine-N-N ' disuccinic acid (HPDDS), diaminoalkyldi (sulfosuccinic acid) (DDS), ethylenedicysteic acid (EDC), ethylenediamine-N-N'-bis (ortho-hydroxyphenyl) acetic acid (EDDHA), N-2-hydroxyethylamine-N, N-diacetic acid, Glyceryliminodiacetic acid, iminodiacetic acid N-2-hydroxypropylsulfonic acid, aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid, β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid N-monoacetic acid, dipicolinic acid, and their salts and / or derivatives, geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), the h higher homologs of up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives, aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs, or nitrilo-tri (methylenephosphonic acid), phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, cyclodextrins, and alkali stannates (sodium stannate), alkali pyrophosphates (tetrasodium pyrophosphate, Disodium pyrophosphate), alkali phosphates (sodium phosphate), and phosphoric acid and salts thereof.

If the composition according to the invention contains both oxidation dye precursors and oxidizing agents as color-changing compounds, these are expediently prepared separately from one another in order to prevent premature, undesired reaction with one another and are brought into contact only immediately before use.

In a further embodiment of the present invention, therefore, agents are preferred which are characterized in that they are prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separately assembled containers, and wherein a container Agent (A) which contains in a cosmetic carrier at least one acrylic acid copolymer according to the invention, and a further container contains an oxidizing agent preparation (B) containing at least one oxidizing agent.

The optionally additionally contained substantive dyes and / or oxidation dye precursors of the developer and / or coupler type are in this case vorteilthafter manner together with the Acyrlsäure copolymer of the invention in compositions (A). In a further embodiment of the present invention, agents are preferred, which are characterized in that they are prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separate prefabricated containers, and wherein a container is an agent (A), which in a cosmetic carrier at least one inventive acrylic acid copolymer and another container contains an agent (B) containing at least one color-altering compound.

The agents according to the invention contain the acrylic acid copolymer (s) and / or the color-changing compound (s) in a cosmetic carrier, preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the agents according to the invention in a powdery or tablet-shaped formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

The preparations according to the invention contain further auxiliaries and additives. Thus, it has proved to be preferred according to the invention if the preparations contain at least one thickener. Both organic and purely inorganic thickening agents can be used. According to a first preferred embodiment, the thickener is an anionic, synthetic polymer which is different from the acrylic acid copolymers according to the invention. Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids, which are obtainable for example under the trade drawing Carbopol ^® commercially. Also preferred is the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially. Further preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. Also preferred are copolymers from Rohm & Haas, sold under the trade name Aculyn ^® 22 as well as by the company National Starch under the trade name Structure ^® 2001, Structure ^® 3001. Preferred anionic copolymers are further Sepigel ^® 305 and Simulgel ^® 600 from SEPPIC and Stabileze ^® QM.

In a further embodiment, the agents according to the invention additionally contain at least one cationic and / or at least one amphoteric polymer.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6)) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol dicaprylate / dicaprate) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-trideceth-6)) are commercially available.

A further preferred cationic polymer is Salcare ^® SC 92nd

Other preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives, cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, in particular under the trade name Cosmedia ^® guar and Jaguar ^® distributed products, polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as with Diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially, vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as the under the names Polyquaternium 2 (eg Mirapol® A-15 from Rhodia), Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Can be used as cationic polymers are sold under the names Polyquaternium-24 (commercial product z. B. Quatrisoft ^® LM 200), known polymers. , Gaffix ^® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

worin

R1, R2, R3, R4, R6

unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,

R5, R5', R5"

unabhängig voneinander für eine C₁-C₂₀-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe stehen,

R7

für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Hydroxyalkylgruppe oder eine C₂-C₆-Polyhydroxyalkylgruppe steht,

n

für eine ganze Zahl von 1 bis 50 000 steht,

m

für eine ganze Zahl von 2 bis 6 steht, und

X^-

für ein physiologisch verträgliches Anion steht.

It is particularly advantageous and thus very particularly preferred if the composition according to the invention additionally contains a cationic acrylic acid ester copolymer which has at least one structural unit of the general formula (A), at least one structural unit of the general formula (B) and at least one structural unit of the general formula Contains (C)

wherein

R1, R2, R3, R4, R6

independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group,

R5, R5 ', R5 "

independently of one another are a C ₁ -C ₂₀ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group,

R7

represents a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group,

n

is an integer from 1 to 50,000,

m

stands for an integer from 2 to 6, and

X ^-

represents a physiologically acceptable anion.

A particularly preferred cationic acrylic ester copolymer is the Polyquaternium-91 known under the INCI name.

Polyquaternium-91 can in this case in an amount of 0.001 to 20 wt .-%, preferably 0.01 to 15 wt .-%, particularly preferably 0.1 to 10 wt .-% and particularly preferably 0.5 to 5 wt. -% be contained in the composition according to the invention.

Another particularly preferred embodiment of the first subject of the invention is therefore an agent for dyeing and / or lightening keratinic fibers, which is characterized in that it additionally - based on its weight - from 0.001 to 20%, preferably 0.01 to 15%, especially preferably 0.1 to 10% and especially preferably 0.5 to 5% polyquaternium-91.

Further cationic polymers according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic. For example, chitosan and its derivatives are preferred as Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB / 101 are freely available commercially, for example under the trade names.

• die im Molekül sowohl freie Aminogruppen als auch freie -COOH- oder SO₃H-Gruppen enthalten und zur Ausbildung innerer Salze befähigt sind,
• zwitterionische Polymere, die im Molekül quartäre Ammoniumgruppen und -COO^--Gruppen oder -SO₃ ^--Gruppen enthalten, sowie
• Polymere, die -COOH-Gruppen oder SO₃H-Gruppen und quartäre Ammoniumgruppen enthalten.

By the term amphoteric polymers are meant such polymers,

• which contain in the molecule both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts,
• zwitterionic polymers containing in the molecule quaternary ammonium groups and -COO ^- groups or -SO ₃ ^- groups, as well as
• Polymers containing -COOH groups or SO ₃ H groups and quaternary ammonium groups.

The quaternary ammonium polymers mentioned in the list are preferably used according to the invention as amphoteric polymers.

An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.

Particularly preferred amphoteric polymers are copolymers of at least one monomer (M1) or (M2) with the monomer (M3), in particular copolymers of the monomers (M2) and (M3). Very particularly preferably used according to the invention amphoteric polymers are copolymers of diallyl dimethyl ammonium chloride and acrylic acid. These copolymers are sold under the INCI name Polyquaternium-22, among others, with the trade name Merquat ^® 280 (Nalco).

Very particularly preferably used according to the invention comonomer based on a comonomer (M4) are terpolymers of diallyldimethylammonium chloride, acrylamide and acrylic acid. These copolymers are marketed ^® under the INCI name Polyquaternium-39, among others, with the trade name Merquat Plus 3330 (Nalco).

In a further preferred embodiment, naturally occurring thickeners are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gum. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are marketed under the trade name Jaguar ^® C from Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ -C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are available under the trade names Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar DC 293 and Jaguar ^{® ®} HP105 Rhone Poulenc.

Also preferred according to this embodiment are biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, vegetable exudate gums such as gum arabic, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar-agar, locust bean gum, pectins, Alginates, starch fractions and derivatives such as Amylose, amylopectin and dextrins, cellulose derivatives such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses.

Preferred hydroxyalkylcelluloses are, in particular, the hydroxyethylcelluloses sold under the names Cellosize ^® Amerchol and Natrosol ^® Hercules. Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ^® by Aqualon, Aquasorb ^® and ambergum ^® from Hercules and Cellgon ^® from Montello.

Starch and its derivatives are also preferred. Natural, plant-derived starches and / or chemically or physically modified starches can be used according to the invention. Especially advantageous is a etherified with 2-hydroxypropyl corn starch as it is, for example, sold by National Starch under the trade name Amaze ^®. But also nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidinone, can be used as thickeners according to the invention. Preferred nonionic, fully synthetic polymers are for example marketed by BASF under the trade name Luviskol ^®. Such nonionic polymers, in addition to their excellent thickening properties, also allow a significant improvement in the sensory feeling of the resulting preparations.

As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the context of the present invention. In particular clays, in particular magnesium aluminum silicates, such as bentonite, especially smectites such as montmorillonite or hectorite, which may optionally be modified also suitable, and synthetic layered silicates such as that sold by Sud Chemie under the trademark Optigel ^® magnesium phyllosilicate, are preferred , With regard to the optionally hydrated SiO ₂ compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds may be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution.

Very particularly preferred according to the invention are water glasses. According to the invention particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

Preferably, an emulsifier or a surfactant is further added to the agent according to the invention, wherein surface-active substances are referred to as surfactants or as emulsifiers, depending on the field of application, and of anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers. These substances will be described in detail below.

Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 C atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain further, nonionic surface-active substances.

Suitable nonionic surfactants are, in particular, C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

• im Wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• im Wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• im Wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• im Wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen oder
• im Wesentlichen aus C₁₆ bis C₁₈-Alkylgruppen besteht.

Particularly preferred are those alkyl polyglycosides of the formula RO- (Z) _x , in which R

• essentially C ₈ and C ₁₀ alkyl groups,
• essentially C ₁₂ and C ₁₄ alkyl groups,
• essentially C ₈ - to C ₁₆ -alkyl groups or
• essentially from C ₁₂ to C ₁₆ alkyl groups or
• consists essentially of C ₁₆ to C ₁₈ alkyl groups.

These compounds are characterized in that any mono- or oligosaccharides can be used as the sugar unit Z. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.8.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Further preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

The anionic, nonionic, zwitterionic or amphoteric surfactants are used in amounts of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent ,

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Further according to the invention useful cationic surfactants are the quaternized protein hydrolyzates. A according to the invention particularly suitable compound is sold under the name Tegoamid ^® S 18 commercially available stearamidopropyl dimethylamine is.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In a preferred embodiment, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred.

Dyeing and brightening processes on keratin fibers usually take place in an alkaline environment. However, in order to preserve the keratin fibers as well as the skin as much as possible, the setting of too high a pH value is not desirable. Therefore, it is preferred if the pH of the ready-to-use agent is between 6 and 12, in particular between 7 and 10.5. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group 2-aminoethane-1-ol (monoethanolamine), 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1,3-diol and triethanolamine. However, it has been found in the context of the investigations of the present invention that furthermore preferred agents according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Very particular preference is given to sodium hydroxide and / or potassium hydroxide. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, particularly preferably L-arginine. Arginine, D-arginine, D / L-arginine used as an alkalizing agent according to the invention. Finally, another preferred alkalizing agent is ammonia.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

The additional active ingredients and auxiliaries are preferably used in the agents according to the invention in amounts of from 0.0001 to 10% by weight, in particular from 0.0005 to 5% by weight, based on the total weight of the application mixture.

Another object of the invention is the use of an agent according to the invention for dyeing and / or lightening keratinhalt fibers, especially human hair. Particularly preferred is the use of an agent according to the invention for improving the color elevation of colorants to keratinic fibers and / or for improving the washing stability of dyed keratinic fibers.

For the application of the agents according to the invention is particularly suitable a method for dyeing and / or lightening keratinic fibers, in particular human hair, which is characterized in that an agent of the first subject invention applied to the keratin-containing fibers, 5 to 60 minutes left on the fiber and then rinsed with water or washed out with a shampoo. Preferably, the Contact time of the ready-to-use colorants 5 to 45 minutes, in particular 10 to 40 minutes, particularly preferably 15 to 35 minutes. During the exposure time of the agent on the fiber, it may be advantageous to assist the lightening process by supplying heat. The heat supply can be done by an external heat source, such as warm air of a hot air blower, as well as, especially in a hair lightening on the living subjects, by the body temperature of the subject. In the latter case, the coloring and / or brightening part is usually covered with a hood. An exposure phase at room temperature is also according to the invention. In particular, the temperature during the exposure time between 20 ° C and 40 ° C, in particular between 25 ° C and 38 ° C. After the end of the exposure time, the remaining dyeing preparation is rinsed with water or a cleaning agent from the hair. As a cleaning agent can be used in particular commercial shampoo, in particular then can be dispensed with the detergent and the rinsing can be done with water when the brightening agent has a strong surfactant-containing carrier.

The agents according to the invention can be formulated as single-component agents or as multicomponent agents, such as two-component agents or three-component agents, and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component. In the case of an oxidative dyeing process, a dyeing and whitening process in which the whitening cream and the oxidizing agent are initially separate is preferred.

• gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• ein Färbe- und/oder Aufhellmittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• dieses Mittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird
• und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von 2 bis 25 Minuten wieder abgespült wird,

wobei das Mittel M2 ein erfindungsgemäßes Mittel ist.Another object of the present invention is therefore a process for dyeing and / or lightening keratinischen fibers, which is characterized in that

• if desired, a pretreatment agent M1 is applied to the fiber, then
• a dyeing and / or whitening agent M2 is applied to the fiber, wherein, if desired, a further agent M3 is added to the agent M2 before application,
• this agent M2 is rinsed from the fiber after 5-30 minutes
• and after the treatment optionally a M4 after-treatment agent is applied to the fiber and rinsed off after a contact time of 2 to 25 minutes,

wherein the agent M2 is an agent according to the invention.

With regard to further preferred embodiments of the methods and uses according to the invention, mutatis mutandis the statements made regarding the agents according to the invention apply.

The following examples are intended to illustrate the subject matter of the present application without, however, limiting it in any way.

embodiments 1. Intensification of the paint elevator

The following formulations were prepared. The quantities are, unless otherwise stated, each in percent by weight. V1 and V2 are comparative formulations, E1 and E2 represent the corresponding formulations according to the invention. raw materials V1 E1 V2 E2 Lanette D. 9.00 9.00 8.10 8.10 Lorol tech. 3.10 3.10 2.80 2.80 Texapon NSO 11.0 11.0 10.00 10.00 Plantapon LGC 5.55 5.55 5.00 5.00 Eumulgin B1 0.28 0.28 0.25 0.25 Ceteareth-20 0.50 0.50 0.25 0.25 Iso-stearic acid 2.22 2.22 2.00 2.00 Myristic acid 98-100 0.56 0.56 0.50 0.50 Product W 37194 2.00 2.00 1.00 1.00 Potassium hydroxide 50% 1.63 1.63 1.20 1.20 Syntran PC 5330 --- 5.00 --- 5.00 p-toluenediamine, sulfate 1.15 1.15 1.08 1.08 2,4,5,6-tetraaminopyrimidine, sulfate 1.10 1.10 1.02 1.02 resorcinol 0.14 0.14 0.11 0.11 2-methyl 0.60 0.60 0.54 0.54 2-amino-3-hydroxypyridine 0.41 0.41 0.40 0.40 2,7-dihydroxynaphthalene 0.03 0.03 0.03 0.03 4-amino-3-nitrophenol 0.01 0.01 --- --- 2 - benzoic acid [(4-amino-2-nitrophenyl) amino] --- --- 0.09 0.09 Sodium sulfite, anhydrous, 96% 0.30 0.30 0.50 0.50 ascorbic acid 0.05 0.05 0.40 0.40 Ammonium sulfate techn. purely 0.30 0.30 0.30 0.30 Sodium silicate 40/42 0.50 0.50 0.50 0.50 1-hydroxyethane-1,1-diphosphonic acid 60% 0.20 0.20 0.20 0.20 Ammonia 25% 7.10 7.10 7.10 7.10 water ad 100 ad 100 ad 100 ad 100

Dyeing creams V1 and E1 were mixed immediately before use with the following oxidizing agent preparation (Ox 1) in the ratio 1: 1:

Ox 1

raw material amount EDTA, disodium salt 0.15 disodiumpyrophosphate 0.30 sodium benzoate 0.04 Emulgade F 2.10 Hydrogen peroxide 50% 12,00 water ad 100

Dyeing creams V2 and E2 were mixed with the following oxidizing agent preparation (Ox 2) in the ratio 1: 1 immediately before use:

Ox 2

raw material amount Caustic soda 45% techn. 0.73 dipicolinic 0.10 disodiumpyrophosphate 0.03 1-hydroxyethane-1,1-diphosphonic acid 60% 1.50 Texapon NSO 2.00 Dow Corning DB 110 A (non-ionic silicone emulsion) 0.07 Aculyn 33A 12,00 Hydrogen peroxide 50% 12,00 water ad 100

Aculyn^® 33A

ca. 28% Festkörper in Wasser; INCI-Bezeichnung: Acrylates Copolymer

Lanette^® D

C_16-18-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis)

Lorol^® tech.

C_12-18-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis)

Texapon^® NSO

Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)

Plantapon^® LGC

ca. 28-34% Aktivsubstanzgehalt in Wasser; INCI-Bezeichnung: Lauryl Glucose Carboxylate, Lauryl Glucoside (Cognis)

Eumulgin^® B 1

Cetylstearylalkohol mit ca. 12-EO-Einheiten (INCI-Bezeichnung: Ceteareth-12) (Cognis)

Emulgade F

INCI-Bezeichnung: Cetearyl Alcohol, Alcohol, PEG-40 Castor Oil, Sodium Cetearylsulfate

Ceteareth-20

Fettsäurealkohole, C16-C18, ethoxyliert (20 EO)

Produkt W 37194

1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-2-propenyl)amino]-, chloride, Polymer mit Natrium 2-Propenoat (INCI-Bezeichnung: Acrylamidopropyltrimoniumchloride/Acrylates Copolymer)

Syntran PC 5330

Polyquaternium-91 (14 Gew.-%) und Polyacrylat-15 (4 Gew.-%)

List of raw materials used

Aculyn ^® 33A

about 28% solids in water; INCI name: Acrylates Copolymer

Lanette ^® D

C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

Lorol® ^® tech.

C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)

Texapon.RTM ^® NSO

Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

Plantapon ^® LGC

about 28-34% active ingredient content in water; INCI name: Lauryl Glucose Carboxylate, Lauryl Glucoside (Cognis)

Eumulgin ^® B 1

Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis)

Emulgade F

INCI name: Cetearyl Alcohol, Alcohol, PEG-40 Castor Oil, Sodium Cetearyl Sulfate

Ceteareth-20

Fatty Acid Alcohols, C16-C18, ethoxylated (20 EO)

Product W 37194

1-Propanaminium, N, N, N-trimethyl-3 - [(1-oxo-2-propenyl) amino] -, chloride, polymer with sodium 2-propenoate (INCI name: Acrylamidopropyltrimoniumchloride / Acrylates Copolymer)

Syntran PC 5330

Polyquaternium-91 (14% by weight) and polyacrylate-15 (4% by weight)

Lv, av, bv

Farbmetrikwerte vor dem Färben

Ln, an, bn

Farbmetrikwerte nach dem Färben

Bestimmung des Farbaufzugsvermögens L a b ΔE Euronaturhaar weiß, ungefärbt vor dem Färben 70,50 2,55 21,11 Färbung mit V1 nach dem Färben 21,92 12,29 6,97 51,5 Färbung mit E1 nach dem Färben 19,98 12,39 6,60 53,5 Färbung mit V2 nach dem Färben 20,82 11,62 5,02 53,0 Färbung mit E2 nach dem Färben 18,89 9,93 4,07 54,9 Before the dyeing process hair strands (Euro Natural Hair White) were measured colorimetrically (Spectralflasch SF 450 colorimetric device from Datacolor). Subsequently, the ready-to-use dyeing formulations prepared as described above were applied to the hair strands and left there at room temperature for 30 minutes. The hair strands were then rinsed thoroughly and dried in a stream of air. After dyeing and drying, the hair strands were again measured colorimetrically. According to the following formula, the color difference (ΔE) between undyed and dyed streak was calculated: $$\mathrm{\Delta }e=\sqrt{{\left(\mathit{lv}-\mathit{ln}\right)}^2+{\left(\mathit{av}-\mathit{at}\right)}^2+{\left(\mathit{bv}-\mathit{bn}\right)}^2}$$

L v , a v , b v

Colorimetry values before dyeing

L n , a n , b n

Colorimetric values after dyeing

Determination of the color absorption capacity L a b AE Euronatur hair white, undyed before dyeing 70.50 2.55 21.11 Staining with V1 after dyeing 21.92 12.29 6.97 51.5 Staining with E1 after dyeing 19.98 12.39 6.60 53.5 Staining with V2 after dyeing 20.82 11.62 5.02 53.0 Staining with E2 after dyeing 18,89 9.93 4.07 54.9

The larger the color difference between undyed streak and colored streak, the stronger is the color lift resulting from the staining. When using the formulations E1 and E2 according to the invention, in each case a significantly more intense color result was obtained in comparison with the corresponding comparison formulation.

2. Improvement of wash fastness

To determine the wash fastness or the color retention, the hair strands dyed with the formulations V2 and E2 under point 1 were placed in an ultrasonic bath and subjected to hairwashing by a standardized method 6, 12, 18 and 24. After 6 washes, the strands were removed from the ultrasonic bath, dried and measured colorimetrically.

L ₀ , a ₀ , b ₀

Farbmetrikwerte nach 0 Haarwäschen

L _x , a _x , b _x

Farbmetrikwerte jeweils nach 6, 12, 18 bzw. 24 Haarwäschen

Bestimmung der Waschechtheiten Haarwäschen (HW) L a b ΔE V2 0 20,82 11,62 5,02 6 21,97 14,62 7,39 4,0 12 21,75 14,35 7,08 3,5 18 21,96 14,35 6,90 3,5 24 23,40 15,70 8,96 6,2 E2 0 18,89 9,93 4,07 6 19,43 11,95 5,50 2,5 12 19,44 12,51 5,92 3,2 18 19,44 12,65 6,08 3,4 24 19,88 13,11 6,56 4,2 In this way, the colorimetric data were determined directly after staining the hair strands (0 HW) and after 6, 12, 18 and 24 washes. In accordance with the following formula, the color difference (ΔE value) between the unwashed and the defined washed strand was calculated in each case: $$\mathrm{\Delta }e=\sqrt{{\left(L_0-{\mathit{L}}_x\right)}^2+{\left({\mathit{a}}_0-{\mathit{a}}_x\right)}^2+{\left({\mathit{b}}_0-{\mathit{b}}_x\right)}^2}$$

L ₀ , a ₀ , b ₀

Colorimetric values after 0 hair washes

L _x, a _x, b _x

Colorimetric values in each case after 6, 12, 18 or 24 hair washes

Determination of wash fastness Hair washes (HW) L a b AE V2 0 20.82 11.62 5.02 6 21.97 14.62 7.39 4.0 12 21.75 14.35 7.08 3.5 18 21.96 14.35 6.90 3.5 24 23,40 15.70 8.96 6.2 E2 0 18,89 9.93 4.07 6 19.43 11,95 5.50 2.5 12 19.44 12.51 5.92 3.2 18 19.44 12.65 6.08 3.4 24 19,88 13.11 6.56 4.2

The greater the color difference (ΔE value) between unwashed and washed tress, the worse is its wash fastness. A comparison of the stained with the formulations V2 and E2 strands shows that the dyed with the inventive formulation E2 strands have a smaller color difference and thus better wash fastness in all washing cycles.

Claims (15)

Agent for dyeing and / or lightening keratinic fibers, in particular human hair, containing in a cosmetic carrier (a) at least one acrylic acid copolymer comprising at least one structural unit of the general formula (I), at least one structural unit of the general formula (II) and at least one structural unit of the general formula (III),

wherein R _1, R 2, R 4 independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, R 3 is a C ₁ -C ₂₀ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group, R5 represents a hydrogen atom, a C ₁ -C ₆ -alkyl group or a phenyl group, M stands for a hydrogen atom or for sodium, potassium, ½ magnesium or ½ calcium, and (b) at least one color-changing compound. Composition according to claim 1, characterized in that the acrylic copolymer containing in the middle at least one structural unit of the general formula (I), at least one structural unit of the general formula (IIa), at least one structural unit of the general formula (IIb), at least one structural unit of contains general formula (IIc), at least one structural unit of general formula (IIIa) and at least one structural unit of general formula (IIIb),

wherein R _1, R 2 ', R 2 ", R 2"', R _{4 ',} R 4 "independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, R 3 ', R 3 ", R 3"' independently of one another represent a C ₁ -C ₂₀ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group, R5 ', R5 "independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group or a phenyl group, M represents a hydrogen atom or represents sodium, potassium, ½ magnesium or ½ calcium, with the proviso that R3 ', R3 "and R3"' represent different radicals from one another and
with the proviso that R5 'and R5 "represent radicals other than one another. Composition according to Claim 2, characterized in that the radicals R 1, R 2 'and R 3' represent a methyl group, the radicals R 2 ", R 2"', R 4', R 4 "and R 5 'represent a hydrogen atom, R 3" denotes an ethyl group R3 "'is an n-butyl group and R5" is a phenyl group. Agent according to one of claims 1 to 3, characterized in that it contains as the acrylic acid copolymer polyacrylate-15. Agent according to one of claims 1 to 4, characterized in that it or the acrylic acid copolymer (s) (a) in a total amount of 0.001 to 25 wt .-%, preferably from 0.01 to 15 wt .-% , particularly preferably from 0.1 to 10% by weight and more preferably from 0.5 to 5% by weight, based on the ready-to-use agent. Agent according to one of claims 1 to 5, characterized in that it contains as color-changing compound at least one oxidation dye precursor and / or at least one substantive dye, in each case in an amount of 0.001 to 12 wt .-%, preferably from 0.01 to 10 wt. -%, particularly preferably from 0.1 to 5 wt .-% and particularly preferably from 0.25 to 3 wt .-% - based on the ready-to-use agent - contains. Agent according to one of claims 1 to 6, characterized in that it contains as color-changing compounds one of the following developer / coupler combinations: p-toluenediamine / resorcinol; p-toluenediamine / 2-methylresorcinol; p-toluenediamine / 2-amino-3-hydroxypyridine; p-toluenediamine / 2,7-dihydroxynaphthalene; p-toluenediamine / 3-aminophenol; p-toluenediamine / 1-naphthol; p-toluenediamine / 1,5-dihydroxynaphthalene; p-toluenediamine / 5-amino-2-methylphenol; p-toluenediamine / 2- (2,4-diaminophenoxy) ethanol; p-toluenediamine / 3-amino-2-chloro-6-methylphenol; p-toluenediamine / 2,6-dihydroxy-3,4-dimethylpyridine; p-toluenediamine / 3-amino-2-methylamino-6-methoxypyridine; p-toluenediamine / 1,3-bis (2,4-diaminophenyl) propane; 2,4,5,6-tetraaminopyrimidine / resorcinol; 2,4,5,6-tetraaminopyrimidine / 2-methylresorcinol; 2,4,5,6-tetraaminopyrimidine / 2-amino-3-hydroxypyridine; 2,4,5,6-tetraaminopyrimidine / 2,7-dihydroxynaphthalene; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / resorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-methylresorcinol; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2-amino-3-hydroxypyridine; 4,5-diamino-1- (2-hydroxyethyl) pyrazole / 2,7-dihydroxynaphthalene; p-aminophenol / resorcinol; p-aminophenol / 2-methylresorcinol; p-aminophenol / 2-amino-3-hydroxypyridine; p-aminophenol / 2,7-dihydroxynaphthalene; p-aminophenol / 3-aminophenol; p-aminophenol / 1-naphthol; p-aminophenol / 1,5-dihydroxynaphthalene; p-aminophenol / 5-amino-2-methylphenol; p-aminophenol / 2- (2,4-diaminophenoxy) ethanol; p-aminophenol / 3-amino-2-chloro-6-methylphenol; p-aminophenol / 2,6-dihydroxy-3,4-dimethylpyridine; p-aminophenol / 3-amino-2-methylamino-6-methoxypyridine; p-aminophenol / 1,3-bis (2,4-diaminophenyl) propane. Agent according to one of claims 1 to 7, characterized in that it contains as color-changing compounds one of the following combinations of two developers and a coupler: p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / resorcinol; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2-methylresorcinol; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2-amino-3-hydroxypyridine; p-toluenediamine / 2,4,5,6-tetraaminopyrimidine / 2,7-dihydroxynaphthalene. Agent according to one of claims 1 to 8, characterized in that it contains as color-changing compound at least one nonionic substantive dye from the group HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1 , Disperse Violet 4, Disperse Black 9, 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4 - (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- ( 2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino ] benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino Contains 3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol. Agent according to one of claims 1 to 9, characterized in that it contains the substantive dye 4-amino-3-nitrophenol either alone or in combination with other color-changing compounds as a color-changing compound. Agent according to one of claims 1 to 10, characterized in that it contains as color-changing compounds both a direct dye and a oxidation dye precursor of the developer type and / or coupler type. Agent according to one of claims 1 to 11, characterized in that it contains as color-changing compound at least one oxidizing agent selected from hydrogen peroxide and its solid addition products of organic or inorganic Compounds, in an amount of 0.001 to 12 wt .-%, preferably from 0.01 to 10 wt .-%, preferably 1 to 9 wt .-%, particularly preferably 2.5 to 8 wt .-% and in particular 3 to 6 wt .-% - based on the ready-to-use agent - contains. Composition according to one of claims 1 to 12, characterized in that it additionally - based on its weight - 0.001 to 20%, preferably 0.01 to 15%, more preferably 0.1 to 10% and particularly preferably 0.5 to 5 Contains% Polyquaternium-91. Use of a composition according to any one of claims 1 to 13 for improving the dyeing of colorants on keratinic fibers and / or for improving the washing stability of dyed keratinic fibers. Process for dyeing and / or lightening keratinic fibers, characterized in that - If desired, a pretreatment agent M1 is applied to the fiber, then a dyeing and / or whitening agent M2 is applied to the fiber, wherein, if desired, a further agent M3 is added to the agent M2 before application, - This agent M2 is rinsed from the fiber after a time of 5-30 minutes - and after the treatment optionally an aftertreatment agent M4 applied to the fiber and rinsed again after a contact time of 2-25 minutes,
wherein the means M2 is an agent according to the invention according to one of claims 1 to 13.